US5205862A - Water resistant ink compositions and process for preparation - Google Patents
Water resistant ink compositions and process for preparation Download PDFInfo
- Publication number
- US5205862A US5205862A US07/844,877 US84487792A US5205862A US 5205862 A US5205862 A US 5205862A US 84487792 A US84487792 A US 84487792A US 5205862 A US5205862 A US 5205862A
- Authority
- US
- United States
- Prior art keywords
- water
- compound
- ink composition
- resistant ink
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
Definitions
- the present invention relates to an aqueous ink composition, more particularly an aqueous ink composition which has excellent water resistance on paper and aging resistance as inks for writing tools, plotter pens or ink jet printers.
- Pigment type aqueous inks containing pigments are popular, but these inks lack stability when in the form of a dispersion and exhibit problems of aging resistance manifested by sedimentation of the pigment particles.
- the present inventors have conducted research on the so-called aqueous ink compositions using a water soluble dye which has excellent aging resistance as compared with pigments and have excellent water-resistance on paper.
- the aforementioned compound is sparingly soluble in water, so that only a dispersion type ink can be obtained.
- the present inventors have found that among the aforementioned compounds, the compounds having a solubility of 5% by weight or more in ethanol at 20° C. are preferred as they are solubilized very easily with an anionic dye having a surface tension in the range of 60 dyn/cm or less at 20° C. measured as a 0.1% by weight aqueous solution.
- Applicants have discovered an aqueous ink which has excellent aging resistance and has an excellent water-resistance on paper.
- the present invention resides in a water-resistant ink composition
- a water-resistant ink composition comprising:
- a water-resistance modifier which contains as an effective component a sparingly water-soluble compound comprising at least one oleophilic group selected from the group consisting of an aromatic ring and an aliphatic hydrocarbon having 6-12 carbon atoms, and at least one hydrophilic group having at least one of O, N and S atoms.
- the water-resistant ink composition contains an anionic dye having a surface tension in the range of 60 dyn/cm or less at 20° C. measured as a 0.1% by weight aqueous solution.
- the water-resistance modifier preferably comprises an effective amount of a sparingly water-soluble compound which contains at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms and at least one hydrophilic group having at least one of O, N and S atoms and which has a solubility of 5% by weight or more in ethanol at 20° C.
- a sparingly water-soluble compound which contains at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms and at least one hydrophilic group having at least one of O, N and S atoms and which has a solubility of 5% by weight or more in ethanol at 20° C.
- the sparingly water-soluble compound can be one or more of the compounds selected from the group consisting of
- water-resistant ink compositions according to the invention prefferably have incorporated therein one or more dry-up resistance imparting agents such as an alcohol, an amine, a urea compound, 2-pyrrolidone, polyvinyl pyrrolidone, sorbitol and dimethylsulfone.
- dry-up resistance imparting agents such as an alcohol, an amine, a urea compound, 2-pyrrolidone, polyvinyl pyrrolidone, sorbitol and dimethylsulfone.
- the urea compound suitable for purposes of the invention include one or more selected from urea, thiourea, ethylene urea, hydroxypropylurea, hydroxyethylurea, ethylene thiourea and diethylthiourea.
- Another aspect of the invention resides in a process for preparing a water-resistant ink composition comprising blending together
- a water-resistance modifier which contains an effective amount of a sparingly water-soluble compound comprising at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms and at least one hydrophilic group having at least one of O, N and S atoms,
- the aliphatic hydrocarbon group preferably includes an alkylene group.
- the step of forming a solution is conducted at a temperature not lower than room temperature.
- a sparingly water-soluble compound containing at least one hydrophilic group which has at least one highly electronegative atom such as O, N or S will form hydrogen bonds between paper and a dye and between the sparingly water-soluble compound and paper which are stronger than the conventional hydrogen bond between paper and a dye and will further improve the water-resistance on paper because of the hydrophobic properties of the sparingly water-soluble compound.
- an anionic dye having a surface tension of 60 dyn/cm or less at 20° C. measured as a 0.1% by weight aqueous solution will form a micell which solubilizes the sparingly water-soluble compound.
- a compound having a solubility of 5% by weight or more in ethyl alcohol among the sparingly water-soluble compounds is preferably solubilized.
- the anionic dyes used according to the present invention and having a surface tension of 60 dyn/cm or less at 20° C. measured as a 0.1% by weight aqueous solution include: Acid dyes:
- Epoxydized C.I. Direct Black 154 Epoxydized C.I. Direct Black 154.
- the aforementioned dyes may be used alone or as a combination of the two or more.
- the sparingly water-soluble compound used according to the present invention and comprising at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms and at least one hydrophilic group selected from the groups having at least one of O, N and S atoms includes one or more of the compounds selected from the group consisting of:
- compound (a) examples include diethyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate or the like.
- compound (b) examples include benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxy-benzophenone or the like.
- the compound (c) include ethyl 2,2-bis(4'-hydroxyphenyl)propane gallate, n-propyl gallate, isoamyl gallate salicylic aidoxime, diethyl 4-hydroxy-1,2-phthalate, para-tert-butylphenol or the like.
- Specific examples of the compound (d) include benzimidazole or the like.
- compound (e) examples include 2-chloro-benzothiazole, 2-methyl-5-chlorobenzothiazole, 2-mercaptobenzothiazole or the like.
- compound (f) examples include benzoin methyl ether or the like.
- the compound (g) examples include propyl p-hydroxybenzoate, phenyl benzoate or the like.
- the compounds described above may be used alone or as a combination of the two or more.
- the ink according to the present invention contains water as a solvent component.
- water as a solvent component.
- the following materials are incorporated for the purpose of preventing the drying of the ink, improving the solubility of dyes, the resistance to drying-up of the ink is improved: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, polyglycerol, polyethylene glycol, polypropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, 2-pyrrolidone, triethanolamine, urea and derivatives thereof.
- the urea derivatives include thiourea, ethylene urea, hydroxyethylurea, hydroxypropylurea, ethylene thiourea, diethyl thiourea and the like.
- the ink according to the present invention can appropriately contain, in addition to the above-described components, additives, for example
- preservatives such as methyl p-hydroxybenzoate or 1,2-benzisothiazolin-3-one;
- rust preventives such as benzotriazole or diethylamine butoxyethyl acid phosphate
- viscosity modifiers such as water-soluble resins including polyvinyl pyrrolidone, polyvinyl alcohol, cellulose derivatives or maleic acid derivatives;
- surface tension modifiers such as surfactants or the like.
- retention modifiers such as polymer emulsions for improving the retention of ink in a non-permeable support such as polyester films or the like, provided that they do not impair the properties of the ink.
- the solution is preferably formed with stirring at room temperature or higher, particularly at 80° C. or above.
- Examples 1-6 the addition of various kinds of glycols were intended to increase the solubility of dyes and the wettability of inks and to improve the resistance to drying-up. However, this addition did not result in the solubilization of the water-resistance imparting agent.
- two or more kinds of dyes can be used as a mixture.
- two or more kinds of dyes can be used as a mixture.
- Viscosity measured at 20° C. with a B type viscometer (TOKYO KEIKI).
- the ink of the present invention is, as apparent from the aforementioned comparison tests, excellent in water-resistance on paper and aging resistance and suitable for inks for writing tools, plotter pens or ink jet printers.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
A water-resistant ink composition containing water, an anionic dye and a water-resistance modifier which contains as an effective component a sparingly water-soluble compound comprising at least one oleophilic group selected from the group consisting of an aromatic ring and an aliphatic hydrocarbon having 6-12 carbon atoms, and at least one hydrophilic group having at least one of O, N and S atoms.
Description
This application is a continuation of application Ser. No. 07/599,902, filed Oct. 19, 1990, now abandoned.
The present invention relates to an aqueous ink composition, more particularly an aqueous ink composition which has excellent water resistance on paper and aging resistance as inks for writing tools, plotter pens or ink jet printers.
A variety of investigations and developments have been hitherto carried out for the purpose of affording water resistance on paper to written matter. Pigment type aqueous inks containing pigments are popular, but these inks lack stability when in the form of a dispersion and exhibit problems of aging resistance manifested by sedimentation of the pigment particles.
The present inventors have conducted research on the so-called aqueous ink compositions using a water soluble dye which has excellent aging resistance as compared with pigments and have excellent water-resistance on paper.
The present inventors have discovered that an anionic dye ink to which has been added a sparingly water-soluble compound containing at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms and at least one hydrophilic group selected from a group having at least one atom such as O, N or S remarkably improves the water resistance on paper.
However, the aforementioned compound is sparingly soluble in water, so that only a dispersion type ink can be obtained. On the other hand, the present inventors have found that among the aforementioned compounds, the compounds having a solubility of 5% by weight or more in ethanol at 20° C. are preferred as they are solubilized very easily with an anionic dye having a surface tension in the range of 60 dyn/cm or less at 20° C. measured as a 0.1% by weight aqueous solution.
Applicants have discovered an aqueous ink which has excellent aging resistance and has an excellent water-resistance on paper.
The present invention resides in a water-resistant ink composition comprising:
(a) water,
(b) an anionic dye, and
(c) a water-resistance modifier which contains as an effective component a sparingly water-soluble compound comprising at least one oleophilic group selected from the group consisting of an aromatic ring and an aliphatic hydrocarbon having 6-12 carbon atoms, and at least one hydrophilic group having at least one of O, N and S atoms.
In a further aspect of the invention, the water-resistant ink composition contains an anionic dye having a surface tension in the range of 60 dyn/cm or less at 20° C. measured as a 0.1% by weight aqueous solution.
The water-resistance modifier preferably comprises an effective amount of a sparingly water-soluble compound which contains at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms and at least one hydrophilic group having at least one of O, N and S atoms and which has a solubility of 5% by weight or more in ethanol at 20° C.
In a more detailed aspect, the sparingly water-soluble compound can be one or more of the compounds selected from the group consisting of
(a) a compound having a dicarboxylate structure,
(b) a compound having a benzophenone structure,
(c) a compound having a phenol structure,
(d) a compound having an imidazole structure,
(e) a compound having a benzothiazol structure,
(f) a compound having a benzoin structure, and
(g) a compound having a benzoate structure.
It is advantageous for the water-resistant ink compositions according to the invention to have incorporated therein one or more dry-up resistance imparting agents such as an alcohol, an amine, a urea compound, 2-pyrrolidone, polyvinyl pyrrolidone, sorbitol and dimethylsulfone.
The urea compound suitable for purposes of the invention include one or more selected from urea, thiourea, ethylene urea, hydroxypropylurea, hydroxyethylurea, ethylene thiourea and diethylthiourea.
Another aspect of the invention resides in a process for preparing a water-resistant ink composition comprising blending together
(a) water,
(b) an anionic dye having a surface extension of 60 dyn/cm or less at 20° C. measured as a 0.1% by weight solution in water, and
(c) a water-resistance modifier which contains an effective amount of a sparingly water-soluble compound comprising at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms and at least one hydrophilic group having at least one of O, N and S atoms,
to thereby form a solution. The aliphatic hydrocarbon group preferably includes an alkylene group.
In carrying out the process, the step of forming a solution is conducted at a temperature not lower than room temperature.
Although applicants do not wish to be bound by any theory, the improvement of the water-resistance on paper is believed to be due to the following assumption. A sparingly water-soluble compound containing at least one hydrophilic group which has at least one highly electronegative atom such as O, N or S will form hydrogen bonds between paper and a dye and between the sparingly water-soluble compound and paper which are stronger than the conventional hydrogen bond between paper and a dye and will further improve the water-resistance on paper because of the hydrophobic properties of the sparingly water-soluble compound.
It is also believed that an anionic dye having a surface tension of 60 dyn/cm or less at 20° C. measured as a 0.1% by weight aqueous solution will form a micell which solubilizes the sparingly water-soluble compound.
In this connection, a compound having a solubility of 5% by weight or more in ethyl alcohol among the sparingly water-soluble compounds is preferably solubilized.
The anionic dyes used according to the present invention and having a surface tension of 60 dyn/cm or less at 20° C. measured as a 0.1% by weight aqueous solution include: Acid dyes:
C.I. Acid Yellow 40,
C.I. Acid Orange 51,
C.I. Acid Red 114 and 249,
C.I. Acid Blue 83, 90, 103 and 127,
C.I. Acid Green 25 and 27;
C.I. Direct Black 154, and
Epoxydized C.I. Direct Black 154.
The aforementioned dyes may be used alone or as a combination of the two or more.
The sparingly water-soluble compound used according to the present invention and comprising at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms and at least one hydrophilic group selected from the groups having at least one of O, N and S atoms includes one or more of the compounds selected from the group consisting of:
(a) a compound having a dicarboxylate structure,
(b) a compound having a benzophenone structure,
(c) a compound having a phenol structure,
(d) a compound having an imidazole structure,
(e) a compound having a benzothiazole structure,
(f) a compound having a benzoin structure, and
(g) a compound having a benzoate structure. The compounds having a solubility of 5% by weight or more in ethyl alcohol at 20° C. are preferred.
Specific examples of the compound (a) include diethyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate or the like.
Specific examples of the compound (b) include benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxy-benzophenone or the like.
Specific examples of the compound (c) include ethyl 2,2-bis(4'-hydroxyphenyl)propane gallate, n-propyl gallate, isoamyl gallate salicylic aidoxime, diethyl 4-hydroxy-1,2-phthalate, para-tert-butylphenol or the like.
Specific examples of the compound (d) include benzimidazole or the like.
Specific examples of the compound (e) include 2-chloro-benzothiazole, 2-methyl-5-chlorobenzothiazole, 2-mercaptobenzothiazole or the like.
Specific examples of the compound (f) include benzoin methyl ether or the like.
Specific examples of the compound (g) include propyl p-hydroxybenzoate, phenyl benzoate or the like.
The compounds described above may be used alone or as a combination of the two or more.
The ink according to the present invention contains water as a solvent component. When the following materials are incorporated for the purpose of preventing the drying of the ink, improving the solubility of dyes, the resistance to drying-up of the ink is improved: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, polyglycerol, polyethylene glycol, polypropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, 2-pyrrolidone, triethanolamine, urea and derivatives thereof.
The urea derivatives include thiourea, ethylene urea, hydroxyethylurea, hydroxypropylurea, ethylene thiourea, diethyl thiourea and the like.
These derivatives may be used alone or as a combination of the two or more.
The ink according to the present invention can appropriately contain, in addition to the above-described components, additives, for example
preservatives such as methyl p-hydroxybenzoate or 1,2-benzisothiazolin-3-one;
rust preventives such as benzotriazole or diethylamine butoxyethyl acid phosphate;
viscosity modifiers such as water-soluble resins including polyvinyl pyrrolidone, polyvinyl alcohol, cellulose derivatives or maleic acid derivatives;
surface tension modifiers such as surfactants or the like; or
retention modifiers such as polymer emulsions for improving the retention of ink in a non-permeable support such as polyester films or the like, provided that they do not impair the properties of the ink.
Next, referring to the process for preparing a water-soluble ink according to the present invention briefly, it s sufficient that an anionic dye is completely dissolved in water and a sparingly water-soluble compound is then added to form a solution.
The solution is preferably formed with stirring at room temperature or higher, particularly at 80° C. or above.
After the sparingly water-soluble compound is completely solubilized, other components are added and the mixture is stirred to form a solution of ink.
The present invention is further explained with reference to Examples and Comparative Examples.
______________________________________
C.I. Acid Blue 90 5.0% by weight
(surface tenson: 52.3 dyn/cm)
2,2'-Dihydroxy-4-methoxybenzophenone
2.0
(solubility in ethyl alcohol: 5% by
weight or more)
Demineralized water 71.0
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 1.0
PROXEL XL-2 1.0
100.0
______________________________________
Procedure: After Acid Blue 90 was completely dissolved in demineralized water at 60° C. by stirring, 2,2'-dihydroxy-4-methoxybenzophenone was added to the solution and the mixture was stirred with heating at 80° C. for 1 hour. The remaining components are added, and the mixture was stirred at room temperature for 1 hour and filtered to give a blue ink.
______________________________________
C.I. Acid Blue 90 5.0% by weight
2,2'Bis(4'-hydroxyphenyl)propane
(solubility: 5% by weight or more)
1.0
Demineralized water 68.0
Ethylene glycol 8.0
Diethylene glycol 8.0
Glycerol 4.0
Urea 5.0
PROXEL XL-2* 1.0
100.0
______________________________________
*Propylene glycol water solution (10%) of 1,2benzisothiazolin-3-one (ICI
PLC)
Following the procedure described in Example 1, a blue ink was prepared.
______________________________________
C.I. Acid Blue 90 5.0% by weight
Benzimidazole (solubility: 5% by
2.0
weight or more)
Demineralized water 71.0
Polyethylene glycol #200
20.0
PROXEL XL-2 1.0
Triethanolamine 1.0
100.0
______________________________________
Following the procedure described in Example 1, a blue ink was prepared.
______________________________________
C.I. Acid Blue 90 5.0% by weight
4-Hydroxy-1,2-phthalic acid diethyl
1.0
ester (solubility: 5% by weight or
more)
Demineralized water 72.0
Polyethylene glycol #300
15.0
Glycerol 5.0
Triethanolamine 1.0
PROXEL XL-2 1.0
100.0
______________________________________
Following the procedure described in Example 1, a blue ink was prepared.
______________________________________
C.I. Acid Blue 90 5.0% by weight
Benzoin methyl ether 1.0
(solubility: 5% by weight or more)
Demineralized water 72.0
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 1.0
PROXEL XL-2 1.0
100.0
______________________________________
Following the procedure described in Example 1, a blue ink was prepared.
______________________________________
C.I. Acid Blue 90 5.0% by weight
2-Chlorobenzothiazole
1.0
(solubility: 5% by weight or more)
Demineralized water 72.0
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 1.0
PROXEL XL-2 1.0
100.0
______________________________________
Following the procedure described in Example 1, a blue ink was prepared.
In Examples 1-6, the addition of various kinds of glycols were intended to increase the solubility of dyes and the wettability of inks and to improve the resistance to drying-up. However, this addition did not result in the solubilization of the water-resistance imparting agent.
______________________________________
C.I. Acid Blue 90 5.0% by weight
2,2'-Dihydroxy-4-methoxybenzophenone
2.0
Demineralized water 93.0
100.0
______________________________________
Procedure: After Acid Blue 90 was completely dissolved in demineralized water by stirring at 60° C., 2,2'-dihydroxy-4-methoxybenzophenone was added and the mixture was stirred with heating at 80° C. for 1 hour. After the mixture was left standing, it was filtered to give a blue ink.
While the preparation of the blue inks has been described in Examples 1-7, inks of different colors can be prepared by altering the dyes in the process according to the present invention.
______________________________________
C.I. Direct Black 154
7.5% by weight
(surface tension: 55.1 dyn/cm)
Bis(2,2,6,6-tetramethyl-4-piperidyl)
2.0
sebacate (solubility: 5% by weight or
more)
Demineralized water 66.5
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 3.0
PROXEL XL-2 1.0
100.0
______________________________________
Procedure: After Direct Black 154 was completely dissolved in demineralized water at 60° C. by stirring, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate was added and the mixture was stirred with heating at 80° C. for 2 hours. Next, the remaining components were added, and the mixture was stirred at room temperature for 1 hour, cooled by leaving it standing and filtered to give a black ink.
______________________________________
C.I. Acid Yellow 40 5.0% by weight
(surface tension: 37.4 dyn/cm)
Benzoin methyl ether 1.0
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 1.0
PROXEL XL-2 1.0
Demineralized water 72.0
100.0
______________________________________
Procedure: After Acid Yellow 40 was completely dissolved in demineralized water at 60° C. by stirring, benzoin methyl ether was added and the mixture was stirred with heating at 80° C. for 1 hour. Next, the remaining components were added, and the mixture was stirred at room temperature for 1 hour, cooled by leaving it standing and filtered to give a yellow ink.
In the ink according to the present invention, two or more kinds of dyes can be used as a mixture.
______________________________________
C.I. Acid Red 114 1.5% by weight
(surface tension: 54.4 dyn/cm)
C.I. Acid Yellow 40 1.5
Bis(2,2,6,6-tetramethyl-4-piperidyl)
0.4
sebacate
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 1.0
PROXEL XL-2 1.0
Demineralized water 74.6
100.0
______________________________________
Procedure: After Acid Red 114 and Acid Yellow 40 were completely dissolved in demineralized water at 60° C. by stirring, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate was added and the mixture was stirred with heating at 80° C. for 1 hour. Next, the remaining components were added, and the mixture was stirred at room temperature for 1 hour, cooled by leaving it standing and filtered to give an orange ink.
In the ink according to the present invention, two or more kinds of dyes can be used as a mixture.
______________________________________
C.I. Acid Blue 90 5.0% by weight
p-tert-Butylphenol (solubility:
0.5
5% by weight or more)
Propyl p-hydroxy-benzoate
0.5
(solubility: 5% by weight or more)
Polyethylene glycol #200
20.0
PROXEL XL-2 1.0
Triethanolamine 1.0
Demineralized water 72.0
100.0
______________________________________
Procedure: After Acid Blue 90 was completely dissolved in demineralized water at 60° C. by stirring, p-tert-butylphenol and propyl p-hydroxybenzoate were added and the mixture was stirred with heating at 80° C. for 1 hour. Next, the remaining components were added, and the mixture was stirred at room temperature for 1 hour, cooled by leaving it standing and filtered to give a blue ink.
______________________________________
C.I. Acid Blue 90 5.0% by weight
Demineralized water 73.0
Polyethylene glycol #200
20.0
Triethanolamine 1.0
PROXEL XL-2 1.0
100.0
______________________________________
Procedure: The first two components (Acid Blue 90 and demineralized water) were stirred with heating at 80° C. for 1 hour. Next, the remaining components were added, and the mixture was stirred at room temperature for 1 hour and filtered to give a blue ink.
______________________________________
C.I. Acid Yellow 40 5.0% by weight
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 1.0
PROXEL XL-2 1.0
Demineralized water 73.0
100.0
______________________________________
Procedure: The first two components were stirred with heating at 80° C. for 1 hour. After cooling the mixture by leaving it standing, it is filtered to give a blue ink.
______________________________________
C.I. Direct Black 154
7.5% by weight
Demineralized water 68.5
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 3.0
PROXEL XL-2 1.0
100.0
______________________________________
Procedure: The first two components (Direct Black 154 and demineralized water) were stirred with heating at 80° C. for 2 hours. Next, the remaining components were added, and the mixture was stirred at room temperature for 1 hour and filtered to give a black ink.
______________________________________
C.I. Direct Blue 87 (surface
5.0% by weight
tension: 68.4 dyn/cm)
2,2'-Dihydroxy-4-methoxybenzophenone
2.0
Demineralized water 71.0
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 1.0
Proxel XL-2 1.0
100.0
______________________________________
Following the procedure described in Example 1, a blue ink was obtained.
______________________________________
C.I. Acid Blue 90 5.0% by weight
8-Benzyl-7,7,9,9-tetramethyl-
2.0
3-octyl-1,3,8-triazaspiro[4,5]-
undecane-2,4-dione (solubility:
less than 5% by weight)
Demineralized water 71.0
Ethylene glycol 10.0
Diethylene glycol 10.0
Triethanolamine 1.0
PROXEL XL-2 1.0
100.0
______________________________________
Following the procedure described in Example 1, a blue ink was obtained.
The composition of Examples and Comparative Examples are shown in Tables 1 and 2.
TABLE 1
__________________________________________________________________________
Example
1 2 3 4 5 6 7 8 9 10 11
__________________________________________________________________________
Acid Blue 90 (Surface tension:
5.0
5.0
5.0
5.0
5.0
5.0
5.0 5.0
52.3 dyn/cm)
Direct Black 154 (Surface 7.5
tension: 55.1 dyn/cm)
Acid Yellow 40 (Surface 5.0
1.5
tension: 37.4 dyn/cm)
Acid Red 114 (Surface 1.5
tension: 54.4 dyn/cm)
2,2'-Dihydroxy-4-methoxy-
2.0 2.0
benzophenone (Solubility:
5% by weight or more)
2,2-Bis(4'-hydroxyphenyl)-
1.0
propane (Solubility:
5% by weight or more)
Benzimidazole (Solubility:
2.0
5% by weight or more)
4-Hydroxy-1,2-phthalic 1.0
acid diethyl ester (Solubility:
5% by weight or more)
Benzoin methyl ether 1.0
(Solubility: 5% by weight
or more)
2-Chlorothiazole (Solubility: 1.0
5% by weight or more)
Bis(2,2,6,6-tetramethyl-4-piperidyl) 2.0 0.4
sebacate (Solubility: 5% by weight
or more)
p-tert-Butylphenol 0.5
(Solubility: 5% by weight or more)
Propyl p-hydroxybenzoate 0.5
(Solubility: 5% or more)
Ethylene glycol 10.0
8.0 10.0
10.0 10.0
10.0
10.0
Diethylene glycol
10.0
8.0 10.0
10.0 10.0
10.0
10.0
Glycerol 4.0 5.0
Polyethylene glycol #200
20.0 20.0
Polyethylene glycol #300 15.0
Urea 5.0
Triethanolamine 1.0 1.0
1.0
1.0
1.0 3.0
1.0
1.0
1.0
PROXEL XL-2 1.0
1.0
1.0
1.0
1.0
1.0 1.0
1.0
1.0
1.0
(Antiseptic agent)
Demineralized water
bal-
bal-
bal-
bal-
bal-
bal-
bal-
bal-
bal-
bal-
bal-
ance
ance
ance
ance
ance
ance
ance
ance
ance
ance
ance
__________________________________________________________________________
Note
1: Surface tension is expressed as a value for a 0.1% by weight solution
of a dye in demineralized water.
2: Solubility is expressed as a value in ethyl alcohol (20° C.).
TABLE 2
__________________________________________________________________________
Comparative Example
1 2 3 4 5
__________________________________________________________________________
Acid Blue 90 5.0 5.0
(Surface tension: 52.3 dyn/cm)
Direct Black 154 7.5
(Surface tension: 55.1 dyn/cm)
Acid Yellow 40 5.0
(Surface tension: 37.4 dyn/cm)
Direct Blue 87 5.0
(Surface tension: 68.4 dyn/cm)
2,2'-Dihydroxy-4-methoxybenzophenone
2.0
(Solubility: 5% by weight or more)
8-Benzyl-7,7,9,9-tetramethyl-3-octyl- 2.0
1,3,8-triazaspiro[4,5]undecane-2,4-
dione (Solubility: less than 5% by weight)
Ethylene glycol 10.0 10.0 10.0 10.0
Diethylene glycol 10.0 10.0 10.0 10.0
Polyethylene glycol #200
20.0
Triethanolamine 1.0 1.0 3.0 1.0 1.0
PROXEL XL-2 (Antiseptic agent)
1.0 1.0 1.0 1.0 1.0
Demineralized water balance
balance
balance
balance
balance
__________________________________________________________________________
Note
1: Surface tension is expressed as a value for a 0.1% by weight solution
of a dye in demineralized water
2: Solubility is expressed as a value in ethyl alcohol (20° C.).
The ink compositions prepared in Examples and Comparative Examples were tested with reference to their aging resistance and water-resistance on paper. The results are shown in Table 3.
The blotting of ink and the staining of writing paper were observed upon dipping of a paper which had been just written in ink for a period of 1 minute.
No blotting of ink or no staining of paper,
◯ A little blotting of ink and no staining of paper,
Δ Much blotting of ink and staining of paper, and
X Little trace of written matter.
Physical properties were measured upon leaving standing of the inks at 50° C. for 60 days and compared with those before aging.
The deposition of dyes or water-resistance imparting agent was observed with an optical microscope (magnification: ×100).
Little variation of physical properties before and after aging,
◯ A little variation of physical properties before and after aging, and no deposition,
X Large variation of physical properties before and after aging accompanied with deposition.
Viscosity: measured at 20° C. with a B type viscometer (TOKYO KEIKI).
pH: measured with a pH meter (TOA DENPA KOGYO).
Surface tension: measured with KYOWA KAIMEN KAGAKU surface tensiometer Model CBUPA-3 at 20° C. hour.
TABLE 3
__________________________________________________________________________
Evaluaton in Examples and Comparative Examples
Physical properties
Physical properties after aging
Water-
before aging at 50° C. for 60 days
resistance
Viscosity
S.T. Viscosity
S.T. Microscopic
Aging
Sample on paper
(20° C.)
pH (dyn/cm)
(20° C.)
pH (dyn/cm)
observation
stability
__________________________________________________________________________
Example
1 ◯
2.8 cp
9.2
41.1 2.7 cp
9.1
44.0 ◯
◯
2 ◯
2.5 6.3
42.1 2.7 9.7
45.1 ◯
◯
3 ◯
3.3 9.5
47.7 3.1 9.2
44.7 ◯
◯
4 ◯
3.2 8.5
41.9 3.4 8.3
41.3 ◯
◯
5 ◯
2.5 9.3
42.6 2.3 8.9
42.4 ◯
◯
6 ◯
2.4 9.3
43.6 2.4 8.9
41.3 ◯
◯
7 ◯
2.0 6.1
42.3 1.9 6.0
40.1 ◯
◯
8 ◯
3.7 11.1
40.2 3.4 9.9
40.8 ◯
◯
9 ◯
2.5 8.5
43.7 2.5 8.2
45.2 ◯
◯
10 ◯
2.3 9.9
45.2 2.0 9.2
49.0 ◯
◯
11 ◯
3.1 9.1
35.0 3.2 9.0
33.1 ◯
◯
Comparative
Example
1 Δ
2.9 9.5
46.4 3.0 9.3
46.2 ◯
◯
2 X 2.4 8.6
46.8 2.4 8.4
50.0 ◯
◯
3 Δ
3.2 10.5
47.5 3.2 10.2
46.1 ◯
◯
4 Δ
2.5 9.6
51.6 -- -- -- many deposits
X
5 ◯
3.0 8.3
41.0 -- -- -- many deposits
X
__________________________________________________________________________
The ink of the present invention is, as apparent from the aforementioned comparison tests, excellent in water-resistance on paper and aging resistance and suitable for inks for writing tools, plotter pens or ink jet printers.
Further variations and modifications of the foregoing will be apparent to those skilled in the art and are intended to be encompassed by the appended claims.
Claims (11)
1. A water-resistant ink composition comprising:
(A) water,
(B) an anionic dye selected from the group consisting of C.I. Acid Yellow 40, C.I. Acid Orange 51, C.I. Acid Red 114 and 249, C.I. Acid Blue 83, 90, 103, and 127, C.I. Acid Green 25 and 27, C.I. Direct Black 154, and epoxydized C.I. Direct Black 154, and
(C) a water-resistance modifier which contains as an effective component at least one sparingly water-soluble compound containing at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms, and at least one hydrophilic group having at least one of O, N and S atoms;
wherein said sparingly water-soluble compound is a compound which is one or two of the compounds selected from the group consisting of
(a) a compound having a dicarboxylate structure selected from bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate or bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate;
(b) a compound having a benzophenone structure selected from benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, or 2,4-dihydroxy-benzophenone;
(c) a compound having a phenol structure selected from ethyl 2,2-bis(4'-hydroxyphenyl)propane gallate, n-propyl gallate, isoamyl gallate salicylic aidoxime, diethyl 4-hydroxy1,2-phthalate, or para-tert-butylphenol;
(d) benzimidazole;
(e) a compound having a benzothiazole structure selected from 2-chloro-benzothiazole, 2-methyl-5-chlorobenzothiazole, or 2-mercaptobenzothiazole;
(f) benzoin methyl ether; and
(g) a compound having a benzoate structure selected from propyl p-hydroxybenzoate or phenyl benzoate.
2. A water-resistant ink composition according to claim 1 wherein said water-resistance modifier comprises an amount of a sparingly water-soluble compound, effective to improve the water-resistance of said dye on paper, which contains at least one oleophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6-12 carbon atoms and at least one hydrophilic group having at least one of O, N and S atoms and which has a solubility of 5% by weight or more in ethanol at 20° C.
3. A water-resistant ink composition according to claim 1, further comprising one or more dry-up resistance imparting agents selected from the group consisting of an alcohol, an amine, a urea compound, 2-pyrrolidone, polyvinyl pyrrolidone, sorbitol and diemthylsulfone.
4. A water-resistant ink composition according to claim 3, wherein said urea compound is a member selected from the group consisting of urea, thiourea, ethylene urea, hydroxyethylurea, ethylene thiourea, diethylthiourea and mixtures thereof.
5. The water resistant ink composition according to claim 1, wherein said sparingly water-soluble compound is a compound having a dicarboxylate structure selected from bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate or bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.
6. The water resistant ink composition according to claim 1, wherein said sparingly water-soluble compound is a compound having a benzophenone structure selected from benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, or 2,4-dihydroxy-benzophenone.
7. The water resistant ink composition according to claim 1, wherein said sparingly water-soluble compound is a compound having a phenol structure selected from ethyl 2,2-bis(4'-hydroxyphenyl) propane gallate, n-propyl gallate, isoamyl gallate salicylic aidoxime, diethyl 4-hydroxy-1,2-phthalate, or para-tert-butylphenol.
8. The water resistant ink composition according to claim 1, wherein said sparingly water-soluble compound is benzimidazole.
9. The water resistant ink composition according to claim 1, wherein said sparingly water-soluble compound is a compound having a benzothiazole structure selected from 2-chloro-benzothiazole, 2-methyl-5-chlorobenzothiazole, or 2-mercaptobenzothiazole.
10. The water resistant ink composition according to claim 1, wherein said sparingly water-soluble compound is benzoin methyl ether.
11. The water resistant ink composition according to claim 1, wherein said sparingly water-soluble compound is a compound having a benzoate structure selected from propyl p-hydroxybenzoate or phenyl benzoate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/844,877 US5205862A (en) | 1989-10-26 | 1992-03-03 | Water resistant ink compositions and process for preparation |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-277313 | 1989-10-26 | ||
| JP1277313A JPH0678495B2 (en) | 1989-10-26 | 1989-10-26 | Water resistant ink composition |
| US59990290A | 1990-10-19 | 1990-10-19 | |
| US07/844,877 US5205862A (en) | 1989-10-26 | 1992-03-03 | Water resistant ink compositions and process for preparation |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US59990290A Continuation | 1989-10-26 | 1990-10-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5205862A true US5205862A (en) | 1993-04-27 |
Family
ID=27336441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/844,877 Expired - Lifetime US5205862A (en) | 1989-10-26 | 1992-03-03 | Water resistant ink compositions and process for preparation |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US5205862A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6031019A (en) * | 1997-02-07 | 2000-02-29 | Kao Corporation | Aqueous ink for ink-jet printing |
| US6508870B1 (en) * | 1999-08-25 | 2003-01-21 | Kabushiki Kaisha Pilot | Ink for plate pen |
| US20050125916A1 (en) * | 2003-12-11 | 2005-06-16 | Pyles Robert A. | Method of dyeing a plastic article |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4325735A (en) * | 1979-06-22 | 1982-04-20 | Canon Kabushiki Kaisha | Recording liquid composition |
| US4343620A (en) * | 1977-01-24 | 1982-08-10 | Ciba-Geigy Corporation | Propylene oxide polyadducts containing carboxyl groups and their salts |
| US4559162A (en) * | 1981-03-10 | 1985-12-17 | Ciba-Geigy Corporation | Compositions of polymers based on acrylic acid, solvents, surfactants and, if appropriate, silicone oils, their preparation and their use as anti-foams and deaerating agents |
| US4702743A (en) * | 1985-05-16 | 1987-10-27 | Imperial Chemical Industries Plc | Liquid dye preparations anionic dyes and polyalkylene-oxy naphthalene derivatives |
-
1992
- 1992-03-03 US US07/844,877 patent/US5205862A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4343620A (en) * | 1977-01-24 | 1982-08-10 | Ciba-Geigy Corporation | Propylene oxide polyadducts containing carboxyl groups and their salts |
| US4325735A (en) * | 1979-06-22 | 1982-04-20 | Canon Kabushiki Kaisha | Recording liquid composition |
| US4559162A (en) * | 1981-03-10 | 1985-12-17 | Ciba-Geigy Corporation | Compositions of polymers based on acrylic acid, solvents, surfactants and, if appropriate, silicone oils, their preparation and their use as anti-foams and deaerating agents |
| US4702743A (en) * | 1985-05-16 | 1987-10-27 | Imperial Chemical Industries Plc | Liquid dye preparations anionic dyes and polyalkylene-oxy naphthalene derivatives |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6031019A (en) * | 1997-02-07 | 2000-02-29 | Kao Corporation | Aqueous ink for ink-jet printing |
| US6508870B1 (en) * | 1999-08-25 | 2003-01-21 | Kabushiki Kaisha Pilot | Ink for plate pen |
| US20050125916A1 (en) * | 2003-12-11 | 2005-06-16 | Pyles Robert A. | Method of dyeing a plastic article |
| US7175675B2 (en) | 2003-12-11 | 2007-02-13 | Bayer Materialscience Llc | Method of dyeing a plastic article |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0397431B1 (en) | Water-resistant ink composition | |
| US6616741B1 (en) | Aqueous metallic ink composition | |
| EP0168694B1 (en) | Aqueous ink composition | |
| CN108359311B (en) | Aqueous anti-halation ink | |
| CA2032631A1 (en) | Water soluble crayon compositions | |
| US4648884A (en) | Solutions of anionic dyes with alkylene glycol mono-alkyl ethers | |
| EP0425280B1 (en) | Water-resistant ink composition and process for preparation | |
| CN107502120A (en) | A kind of chemically-resistant solvent water varnish good with the dispersion moistening of aqueous pigment color ink compared with suitable intaglio printing by force and preparation method thereof | |
| US5205862A (en) | Water resistant ink compositions and process for preparation | |
| EP0434179B1 (en) | Water-resistant ink composition | |
| JP4235809B2 (en) | Surfactant composition | |
| US4238234A (en) | Printing inks containing a polyether amine fixing agent | |
| JP4645796B2 (en) | Water-soluble surfactant composition, ink and paper coating agent | |
| US7163575B2 (en) | Water-based, resin-free and solvent-free eradicable ball-pen inks | |
| JP2004261679A (en) | Water-soluble surfactant composition | |
| US4384065A (en) | High gloss water-base coating composition | |
| WO2018067829A1 (en) | Pigment dispersion with coalescent | |
| US6312514B1 (en) | Use of diol alkoxylates as additives for the production of pigment concentrates | |
| JPH04331263A (en) | Salt-forming dye, concentrated solution composition thereof, and ink composition | |
| JP3545462B2 (en) | Oil-based blue ink composition | |
| JPH064804B2 (en) | Water based ink | |
| JPH03277671A (en) | Water-based ink composition | |
| JPH04103676A (en) | Water-resistant ink composition and its production | |
| JPS6114270A (en) | Water based ink composition | |
| JPH0621261B2 (en) | Oil-based ink |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: KABUSHIKI KAISHA PILOT 8-1, NISHIGOTANDA 2-CHOME Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KIYOMOTO, HIROSHI;SUGIMOTO, YASUYUKI;REEL/FRAME:006296/0147 Effective date: 19901030 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| AS | Assignment |
Owner name: KABUSHIKI KAISHA PILOT CORPORATION (ALSO TRADING A Free format text: CHANGE OF NAME;ASSIGNOR:KABUSHIKI KAISHA PILOT;REEL/FRAME:015251/0613 Effective date: 20040323 |
|
| FPAY | Fee payment |
Year of fee payment: 12 |